We report a transition from the ferroelectric nematic liquid crystal (NF) phase to a lower-temperature, apolar fluid phase having reentrant isotropic symmetry (IR), in the liquid crystal compound RM734 doped with small concentrations of the ionic liquids 1-Butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) or 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-TFSI). Even a trace amount of ionic liquid dopant facilitates the kinetic pathway for the transition from the NF to the IR, enabling simple cooling to produce this isotropic fluid phase rather than resulting in immediate crystallization. The IR was also obtained in the absence of specific ionic liquid doping by appropriate temperature cycling in three distinct, as-synthesized-and-purified batches of RM734, two commercial and one from our laboratory. Ionic liquid doping also stabilizes the smectic ZA, an additional birefringent antiferroelectric phase having the director parallel to fluid smectic layers, significantly increasing its temperature range between the paraelectric and ferroelectric nematic phases with increasing BMIM concentration.

We report a transition from the ferroelectric nematic liquid crystal (N_F) phase to a lower-temperature, antiferroelectric fluid phase having reentrant isotropic symmetry (I_A), in the liquid crystal compound RM734 doped with small concentrations of the ionic liquids BMIM or EMIM. Even a trace amount of ionic liquid dopant facilitates the kinetic pathway for the transition from the N_F to the I_A, enabling simple cooling to produce this isotropic fluid phase rather than resulting in crystallization. The I_A was also obtained in the absence of specific ionic liquid doping by appropriate temperature cycling in three distinct, as-synthesized-and-purified batches of RM734, two commercial and one from our laboratory. An additional birefringent, lamellar-modulated, antiferroelectric phase with the director parallel to the layers, resembling the smectic Z_A, is found between the paraelectric and ferroelectric nematic phases in RM734/BMIM mixtures.

Physical unclonable functions (PUFs)-a hardware-based security device using randomness-have evolved from basic integrated circuit designs to advanced systems using diverse materials and mechanisms. However, most PUFs are limited by single-factor challenges and fixed key generation, making them vulnerable to brute-force attacks. A reconfigurable and multidimensional liquid crystal (LC)-based PUF is presented integrated into an organic field-effect transistor (OFET) to address limitations. This system combines optical and electrical PUFs through unique optical fingerprint textures and random molecular alignment of the semiconductive smectic LC material. The PUF can be reconfigured by a simple heating and cooling process, overcoming the limitations of fixed-structure PUFs. Furthermore, this approach enhances security by enabling hierarchical authentication due to the multi-response factors, providing robust solutions for anticounterfeiting and cryptographic applications.

The idea that rod-like molecules possessing an electric dipole moment could exhibit a ferroelectric nematic phase was suggested more than a century ago. However, only recently such a phase has been reported for two quite different liquid crystals: RM734 (4-[(4-nitrophenoxy)carbonyl)]phenyl 2,4-dimethoxybenzoate) and DIO (2.3',4',5'-tetrafluoro[1,1'-biphenyl]-4-yl 2.6-difluoro-4-(5-propyl-1,3-dioxan-2-yl) benzoate). For RM734 a direct ferroelectric nematic (NF) to classical nematic N transition was reported, whereas for DIO an intermediate phase Nx was discovered between the NF and the N phases. Here we present high-resolution calorimetric evidence that an intermediate Nx phase also exists in RM734 along a narrow temperature range between the NF and the N phases.

The layered structure of smectic liquid crystals cannot develop unobstructed when confined to spherical shells with layers extending in the radial direction, since the available cross section area increases from the inside to the outside of the shell yet the number and thickness of layers must be constant. For smectic-A (SmA) liquid crystals, with the layer normal m parallel to the director n, the frustration breaks up the texture into spherical lune domains with twist deformations of alternating sense, overlaid with a herringbone-like secondary modulation and mediated via localized bend regions where the boundary conditions are violated. The SmC phase has more degrees of freedom to resolve the frustration thanks to its non-zero tilt angle tau between n and m, but its response to tangential shell confinement was never studied. We show experimentally and theoretically that the lunes in shells undergoing a SmA-SmC transition become twice as wide and half as many and they lose the secondary modulation, adopting a configuration with no layer twist but uniform layer bend if tau reaches a large enough value. Our study expands our understanding of how smectics respond to spherical confinement and it opens new soft matter research opportunities, given the rich diversity of phases with SmC-like symmetry, including chiral and spontaneously polarized phases.

The twist-bend nematic liquid crystal phase is a three-dimensional fluid in which achiral bent molecules spontaneously form an orientationally ordered, macroscopically chiral, heliconical winding of a ten nanometer-scale pitch in the absence of positional ordering. Here, the structure of the twist-bend phase of the bent dimer CB7CB and its mixtures with 5CB is characterized, revealing a hidden invariance of the self-assembly of the twist-bend structure of CB7CB, such that over a wide range of concentrations and temperatures, the helix pitch and cone angle change as if the ground state for a pitch of the TB helix is an inextensible heliconical ribbon along the contour formed by following the local molecular long axis (the director). Remarkably, the distance along the length for a single turn of this helix is given by 2πRmol, where Rmol is the radius of bend curvature of a single all-trans CB7CB molecule. This relationship emerges from frustrated steric packing due to the bent molecular shape: space in the fluid that is hard to fill attracts the most flexible molecular subcomponents, a theme of nanosegregation that generates self-assembled, oligomer-like correlations of interlocking bent molecules in the form of a brickwork-like tiling of pairs of molecular strands into duplex double-helical chains. At higher temperatures in the twist-bend phase, the cone angle is small, the director contour is nearly along the helix axis z, and the duplex chains are sequences of biaxial elements formed by overlapping half-molecule pairs, with an approximately 45° rotation of the biaxis between each such element along the chain.

We have structurally characterized the liquid crystal (LC) phase that can appear as an intermediate state when a dielectric nematic, having polar disorder of its molecular dipoles, transitions to the almost perfectly polar-ordered ferroelectric nematic. This intermediate phase, which fills a 100-y-old void in the taxonomy of smectic LCs and which we term the "smectic ZA," is antiferroelectric, with the nematic director and polarization oriented parallel to smectic layer planes, and the polarization alternating in sign from layer to layer with a 180 Å period. A Landau free energy, originally derived from the Ising model of ferromagnetic ordering of spins in the presence of dipole-dipole interactions, and applied to model incommensurate antiferroelectricity in crystals, describes the key features of the nematic-SmZA-ferroelectric nematic phase sequence.

Here, we report the relationship between helical pitch of the helical nanofilament (HNF) phase formed by bent-core molecule NOBOW and the concentration of achiral dopants 5CB and octane, using linearly polarized resonant soft X-ray scattering (RSoXS). Utilizing theory-based simulation, which fits well with the experiments, the molecular helices in the filament were probed and the superstructure of helical 5CB directed by groove of HNFs was observed. Quantitative pitch determination with RSoXS reveals that helical pitch variation is related to 5CB concentration with no temperature dependence. Doping rodlike immiscible 5CB led to a pitch shortening of up to 30%, which was attributed to a change in interfacial tension. By shedding light not only on phase behavior of binary systems but also enabling control over pitch length, our work may benefit various applications of HNF-containing binary systems, including optical rotation devices, circularly polarized light emitters, and chirality transfer agents.

Bis-1,3-isophthalimines flanked by two side 3-aryl-5-perfluoroalkylisoxazoline or 3-aryl-5-perfluoroalkylisoxazol arms were produced and liquid crystal properties were analysed. Monotropic smectic A mesophase was found for bis-1,3-isophthalimines containing the 3-aryl-5-perfluorooctylisoxazoline (8b). Thermal behaviour was analysed and discussed by DSC, POM, DFT calculations, cohesive energy density (CED), Hildebrand solubility parameters and molecular-shape features. Notably, for long side arm perfluorooctyl 8b, the reduced value of CED is partially compensated by molecular shape of the molecules in the condensed state favouring the SmA mesophase formation.

In high-resolution adiabatic scanning calorimetry (ASC) experiments, data for the temperature dependence of the specific enthalpy, h(T), and of the specific heat capacity, c(p)(T), are simultaneously obtained, from which the order of the phase transition and critical behaviour can be evaluated. ASC was applied to study the nematic to ferroelectric nematic phase transition (N-N-F) in the liquid crystal molecule 4-[(4-nitrophenoxy)carbonyl]phenyl 2,4-dimethoxybenzoate (RM734). The N-N-F was found to be very weakly first order with a latent heat Delta h = 0.115 +/- 0.005 J/g. The pretransitional specific heat capacity behaviour is substantially larger in the high-temperature N phase than in the low-temperature N-F phase. In both phases the power-law analysis of c(p)(T) resulted in a critical exponent alpha = 0.50 +/- 0.05 and amplitude ratio A(NF)/A(N) = 0.42 +/- 0.03. The very small latent heat and the value of alpha indicate that the N-N-F transition is close to a tricritical point. This is confirmed by a value of the order parameter exponent beta approximate to 0.25, recently obtained from electric polarisation measurements. Invoking two-scale-factor universality, it follows from the low value of A(NF)/A(N) ratio that the size of the critical fluctuations is much larger in the N-F phase than in the N phase.

The organic mesogens RM734 and DIO are members of separate molecular families featuring distinct molecular structures. These families, at the present time, are the only ones known to exhibit a ferroelectric nematic liquid crystal (LC) phase. Here we present an experimental investigation of the phase diagram and electro-optics of binary mixtures of RM734 and DIO. We observe paraelectric nematic (N) and ferroelectric nematic (NF) phases in both materials, each of which exhibits complete miscibility across the phase diagram, showing that the paraelectric and ferroelectric are the same phases in RM734 as in DIO. Remarkably, these molecules form ideal mixtures with respect to both the paraelectric-ferroelectric nematic phase behavior and the ferroelectric polarization density of the mixtures, the principal order parameter of the transition. Ideal mixing is also manifested in the orientational viscosity, and the onset of glassy dynamics at low temperature. This behavior is attributable in part to the similarity of their overall molecular shape and net longitudinal dipole moment (~ 11 Debye), and to a common tendency for head-to-tail molecular association. In contrast, the significant difference in molecular structures leads to poor solubility in the crystal phases, enhancing the stability of the ferroelectric nematic phase at low temperature in the mixtures and making possible room temperature electro-optic effects. In the mixtures with excess DIO, an intermediate phase appears via an ultraweak, first-order transition from the N phase, in a narrow temperature range between the paraelectric and ferroelectric nematics.

Significance Liquid crystal science grows in richness and applicability with each new phase that is found or created. The recent discovery of the ferroelectric nematic was both thrilling and unexpected, since it appeared in new molecules not much different in structure from many similar materials studied over the last 100 years. Clearly, significant secrets remain to be discovered in the complexities of organic molecular architecture and interaction. A fundamental question following the ferroelectric nematic discovery was whether there could also be a ferroelectric smectic A, the nematic-companion phase obtained when molecules spontaneously position to form planar, fluid layers normal to their molecular long axes. Here, we report such a phase, broadening the ferroelectric nematic realm.

Correction for 'Surface alignment of ferroelectric nematic liquid crystals' by Federico Caimi et al., Soft Matter, 2021, 17, 8130-8139, https://doi.org/10.1039/D1SM00734C.

We report a three-dimensional (3D) molecular orientation control of a liquid crystal organic semiconductor (LC-OSC) based on the long-range ordering characteristic of an LC material. To this end, a synthetic LC-OSC molecule, MeOPh-BTBT-C8, with a fluidic nematic (N) phase that is essential for alignment control over a large area and a smectic E (SmE) phase showing high ordering, was prepared. A simple flipping of a sandwich cell made of the LC-OSC material between the top and bottom substrates that have uniaxial–planar degenerated alignment as well as crossed rubbing directions responds to the given surface anchoring condition and temperature gradient. Optical observation of the alignment-controlled LC-OSC was carried out by polarized optical microscopy (POM), and the corresponding charge carrier mobility was also measured by fabricating organic field-effect transistors (OFETs). Our platform offers a facile approach for multidirectional and multifunctional organic electronic devices using the stimulus–response characteristics of LC materials.

The recently discovered ferroelectric nematic ( N F ) liquid crystals (LCs) with over 0.04 C m −2 ferroelectric polarization and 10 4 relative dielectric constants, coupled with sub‐millisecond switching, offer potential applications in high‐power super capacitors and low voltage driven fast electro‐optical devices. This paper presents electrical, optical, and electro‐optical studies of a ferroelectric nematic LC material doped with commercially available chiral dopants. While the N F phase of the undoped LC is only monotropic, the chiral N F phase is enantiotropic, indicating a chirality induced stabilization of the polar nematic order. Compared to undoped N F material, a remarkable improvement of the electro‐optical switching time is demonstrated in the chiral doped materials. The color of the chiral mixtures that exhibit a selective reflection of visible light in the chiral N F phase, can be reversibly tuned by 0.02–0.1 V µm −1 in‐plane electric fields, which are much smaller than typically required in full‐color cholesteric LC displays and do not require complicated driving scheme. The fast switchable reflection color at low fields has potential applications for LC displays without backlight, smart windows, shutters, and e‐papers.

Significance The devices of the portable computing revolution are being made possible by nematic liquid crystal display (LCD) technology. The optical changes viewed in a dynamic LCD image are based on reorienting molecules by coupling electronically generated electric fields to molecular dielectric anisotropy. This takes place in appropriate fluid electro-optic structures stabilized by nonpolar orientational coupling of molecules to surfaces. The recent observation of ferroelectric nematics having spontaneous macroscopic electric polarization density has introduced a much stronger polar coupling of electric field to molecular reorientation in nematics. This development opens opportunities for advanced electro-optics, but these will require polar control of molecular orientation by surfaces. The generation of polar-structured surfaces and their coupling to nematic polarity is demonstrated in this paper. We show that surface interactions can vectorially structure the three-dimensional polarization field of a ferroelectric fluid. The contact between a ferroelectric nematic liquid crystal and a surface with in-plane polarity generates a preferred in-plane orientation of the polarization field at that interface. This is a route to the formation of fluid or glassy monodomains of high polarization without the need for electric field poling. For example, unidirectional buffing of polyimide films on planar surfaces to give quadrupolar in-plane anisotropy also induces macroscopic in-plane polar order at the surfaces, enabling the formation of a variety of azimuthal polar director structures in the cell interior, including uniform and twisted states. In a π-twist cell, obtained with antiparallel, unidirectional buffing on opposing surfaces, we demonstrate three distinct modes of ferroelectric nematic electro-optic response: intrinsic, viscosity-limited, field-induced molecular reorientation; field-induced motion of domain walls separating twisted states of opposite chirality; and propagation of polarization reorientation solitons from the cell plates to the cell center upon field reversal. Chirally doped ferroelectric nematics in antiparallel-rubbed cells produce Grandjean textures of helical twist that can be unwound via field-induced polar surface reorientation transitions. Fields required are in the 3-V/mm range, indicating an in-plane polar anchoring energy of wP ∼3 × 10−3 J/m2.

The success of nematic liquid crystals in displays and optical applications is due to the combination of their optical uniaxiality, fluidity, elasticity, responsiveness to electric fields and controllable coupling of the molecular orientation at the interface with solid surfaces. The discovery of a polar nematic phase opens new possibilities for liquid crystal-based applications, but also requires a new study of how this phase couples with surfaces. Here we explore the surface alignment of the ferroelectric nematic phase by testing different rubbed and unrubbed substrates that differ in coupling strength and anchoring orientation and find a variety of behaviors - in terms of nematic orientation, topological defects and electric field response - that are specific to the ferroelectric nematic phase and can be understood as a consequence of the polar symmetry breaking. In particular, we show that by using rubbed polymer surfaces it is easy to produce cells with a planar polar preferential alignment and that cell electrostatics (e.g. grounding the electrodes) has a remarkable effect on the overall homogeneity of the ferroelectric ordering.